CN1039992C - Carboxylic acid derivatives - Google Patents

Carboxylic acid derivatives Download PDF

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CN1039992C
CN1039992C CN93107847A CN93107847A CN1039992C CN 1039992 C CN1039992 C CN 1039992C CN 93107847 A CN93107847 A CN 93107847A CN 93107847 A CN93107847 A CN 93107847A CN 1039992 C CN1039992 C CN 1039992C
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several
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alkyl
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CN1083804A (en
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P·梅恩菲什
T·皮特纳
M·博格
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Novartis AG
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/34—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C07C271/58—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles

Abstract

Compounds of the formula (I) in which A is oxygen, sulfur or -NR1-; B is C2-C6alkylene, D-E is -O-E, -S-E, -O-CH2-E, -O-C(=O)-E, -O-C(=O)-O-E, -O-C(=O)-N(H)-E or -O-C(=S)-N(H)-E; E is phenyl; phenyl which is substituted by one to three substituents; a five-membered aromatic heterocycle having one to three hetero atoms; a five-membered aromatic heterocycle which has one to three hetero atoms and which is substituted by one or two substituents; a six-membered aromatic heterocycle which has one to three nitrogen atoms; or a six-membered aromatic heterocycle which has one to three nitrogen atoms and which is substituted by one or two substituents; L is halogen or methyl; X is fluorine; Y is chlorine or fluorine; Z is hydrogen, fluorine or methyl; m is the number zero, one, two, three, four or five; n is the number zero, one or two and R1 is hydrogen, C1-C4 alkyl, phenylthio or tolylthio, in free form or in salt form, can be used as pesticides and can be prepared in a manner known per se.

Description

Carboxylic acid derivative
The present invention is relevant new ω-vinyl halides alkanoic acid derivs, and their preparation method and intermediate product contain the agricultural chemicals and the application in harmful organism control of these compounds.
According to ω of the present invention-vinyl halides alkanoic acid derivs is the free form shown in the following formula, or the compound of the form of salt when needing
Figure C9310784700071
In formula
A is an oxygen, sulphur or-NR 1-;
B is C 2-C 6Alkylidene group,
D-E is-O-E-S-E ,-O-CH 2-E ,-O-C (=O)-E ,-O-C (=O)-O-E ,-O-C (=O)-N (H)-E or-O-C (=S)-N (H)-E;
E is a phenyl; Be selected from halogen, C by 1 to 3 1-C 4Alkyl, halo-C 1-C 4Alkyl, C 1-C 4Alkoxyl group, halo-C 1-C 4Alkoxyl group, cyano group, the phenyl that the substituting group of nitro and methylene-dioxy replaces; Contain 1 to 3 and be selected from the 5-membered aromatic heterocycle that contains nitrogen, oxygen and sulfur heteroatom; Contain 1 to 3 aromatic heterocycle that is selected from nitrogen, oxygen and sulfur heteroatom, contain 1 to 3 and be selected from nitrogen, oxygen and sulfur heteroatom and be selected from halogen, C by 1 to 2 1-C 4Alkyl and C 1-C 4The 5-membered aromatic heterocycle that the haloalkyl substituting group replaces; The hexa-atomic aromatic heterocycle that contains 1 to 3 nitrogen-atoms; Or contain 1 to 3 nitrogen-atoms and be selected from by halogen C by 1 to 2 1-C 4Alkyl and C 1-C 4The hexa-atomic aromatic heterocycle that the substituting group that haloalkyl is formed replaces;
L is halogen or methyl;
X is a fluorine;
Y is chlorine or fluorine;
Z is a hydrogen, fluorine or methyl;
M is a numeral 0,1,2,3,4 or 5;
N is numeral 0,1 or 2 Hes
R 1Be hydrogen, C 1-C 4-alkyl, thiophenyl or toluene sulfenyl,
EP-A-0432861 proposes the effective constituent use that the halo alkeno derivatives can be used as agricultural chemicals.But the biological property field control harmful organism of the described compound of this document is not exclusively satisfactory, so other compound with agricultural chemicals characteristic need be provided, this target is achieved by Compound I provided by the invention.
If desired, if promptly have at least a basic center to exist in particular compound I, The compounds of this invention I also comprises acceptable salt on the acid salt, particularly agrochemistry so.Suitable acid is hydrochloric acid, Hydrogen bromide, and sulfuric acid, phosphoric acid, nitric acid has identical central atom, but their oxidation level is higher or lower acid such as perchloric acid, nitrous acid or phosphorous acid acetate and succsinic acid.
Except as otherwise noted, used noun implication is as follows in this context.
Be suitable for referring to fluorine and chlorine also has bromine and iodine preferred fluorine and chlorine as substituent halogen atom.Halogen herein is to be understood that itself is a substituting group or a substituent part, for example as the integral part of haloalkyl or halogenated alkoxy.
Except as otherwise noted, carbon-containing group and compound are usually preferred 1 to 4, particularly 1 or 2 carbon atom.
But be suitable as substituent alkyl and alkoxyl group straight or branched.The example that can be used as alkyl group has methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl or the tertiary butyl.The example that is suitable as alkoxy base is methoxyl group particularly, oxyethyl group, propoxy-, isopropoxy or butoxy and their isomer.
If be suitable as substituent alkyl, alkoxyl group or phenyl or aromatic heterocycle are replaced by halogen, and they can only be partially halogenated or perhalogenation.To halogen, the definition that alkyl and alkoxyl group are given can be used for this situation above, and for example the moieties in these groups is by fluorine, and chlorine and/or bromo-replace to trisubstituted methyl, as CHF 2Or CF 3By fluorine, chlorine and/or bromo-replace the ethyl that replaces to five, as CH 2CF 3, CF 2CF 3, CF 2CCl 3, CF 2CHCl 2, CF 2CHF 2, CF 2CFCl 2, CF 2CHBr 2, CF 2CHClF, CF 2CHBrF or CClFCHClF propyl group or sec.-propyl, each in them are by fluorine, and chlorine and/or bromo-replace to seven replacements, as CH 2CHBrCH 2Br, CH 2CHFCF 3, CH 2CF 2CF 3Or CH (CF 3) 2With butyl or its isomer, they each is replaced to nine replacements, as CF (CF by fluorine, chlorine and/or bromo- 3) CHFCF 3Or CH 2(CF 2) 2CF 3Aromatic heterocycle with substituting group, substituting group is possible preferred on a carbon atom of heteroatoms makeup ring shelf structure.Usually, these rings cross on the part D to bridge by a carbon atom bonding on the ring.According to the present invention is the preferred following basic structure of the defined 5-membered aromatic heterocycle of group E: pyrroles, imidazoles, pyrazoles, 1,2, the 3-triazole, 1,2,4-triazole ， oxazole isoxazole, thiazole, isothiazole, 1,2, the 3-thiadiazoles, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, 1,2,3-oxadiazole, 1,2, the 4-oxadiazole is as 1,3, the 4-oxadiazole.According to the present invention, the hexa-atomic aromatic heterocycle that is suitable for as E is a pyridine, pyrimidine, pyrazine, pyridazine, 1,2,4-triazine and 1,3,5-triazines.If these are further replaced for defined aromatic base of E and phenyl, they can be replaced to three replacements by those cited identical or different substituting groups one.The aromatic substituent that replaces preferably has 1 to 2 substituting group.For-defined the aromatic base of D-E also have below separately implication:
Phenoxy group,
Thiophenyl,
3,5-dichloropyridine-2-oxygen base,
Pyridine-2-oxygen base, benzyloxy, 3-chlorophenoxy, 3-methyl isophthalic acid, 2,4-thiadiazoles-5-oxygen base, 4-fluorophenoxy, 3-fluorophenoxy, the 2-fluorophenoxy, 3-chloro-5-trifluoromethyl-pyridine-2-oxygen base, 3-chloro-5-(2,2-two chloro-1,1, the 2-trifluoroethyl)-pyridine-2-oxygen base, 3,5-two fluorophenoxies, 2-ethoxymethyl-1,3,4-thiadiazoles-5-methoxyl group, 3-sec.-propyl-1,2,4-thiadiazoles-5-oxygen base, 4-chlorophenoxy, 2-chloro-4-trifluoromethyl-phenoxy group, 5-bromo thianthrene-2-methoxyl group, 4-4-trifluoromethylphenopendant, 4-ethyl phenoxy group, 4-methoxyl group phenoxy group, 4-chlorinated benzene sulfenyl and 4-chloro benzyloxy, the 4-cyano benzyloxy, 2-nitro benzyloxy
3-nitro benzyloxy,
4-nitro benzyloxy,
The 4-fluorinated benzyloxy,
4-trichloromethyl benzyloxy,
4-methyl benzyloxy,
4-methoxyl group benzyloxy base,
4-tertiary butyl benzyloxy,
4-tertiary butyl phenoxy group.
Group-D-E can occupy the ortho position of phenyl, a position or contraposition.Preferred contraposition.
Because vinyl is in the ω position in the alkenyl-carboxylic on basis, so the definition of formula 1 comprises the 3-butenoic acid, 5-hexenoic acid, 7-olefin(e) acid, 9-decylenic acid, 11-dodecenoic acid and 13-tetradecenoic acid.
Subunit in formula I compound group must be some groups like this, in these subunits groups or
A) A is an oxygen, or
B) B is an ethylene bridge, or
C) A is one a-NH-bridge, or
D) n is a numeral 0, or
E) be-O-, or
F) E is a phenyl, pyridyl, and thiadiazolyl group is selected from cyano-containing, nitro, halogen, C by 1 or 2 1-C 4-alkyl and C 1-C 4The phenyl that-haloalkyl substituting group replaces is selected from by 1 or 2 and contains halogen, C 1-C 4The pyridyl that-alkyl substituent replaces, or C 1-C 4-alkyl thiazolyl, or
G) m is a numeral 0,1 or 4, or
H) Y is that fluorine and Z are hydrogen, or
I) D is-O-CH 2-, or
K) be-O-CO-or-O-CO-O-.
From subunit group in those compounds of definite implication a) preferably compound be that those n are 0, particularly n be 0 and m be 0,1 or 4, especially n is 0, m be 0,1 or 4 and B be the compound of an ethylene bridge.
From subunit group by in those compounds of definite implication a) preferably compound be those n be 0 and D be that oxygen or sulphur, particularly n are 0, D is that oxygen or sulphur and B are ethylene bridge, especially n is 0, D is oxygen or sulphur, and B is that an ethylene bridge and m are 0,1 or 4 compounds.
From subunit group by those compounds of a) definite implication preferably compound be that those D are-O-CH 2-, particularly D is-O-CH 2-, n is that O and B are ethylene bridge, especially D is-O-CH 2-, n is 0, B is that ethylene bridge and m are 0,1 or 4 compounds.
From subunit group in those compounds of definite implication a) preferably compound be those D be-O-CO-or-O-CO-O-, particularly D for-O-CO-or-O-CO-O-and n are 0, especially D be-O-CO-or-O-CO-O-, n is 0, B is that ethylene bridge and m are 0,1 or 4 compounds.
Be e from subunit group) in those compounds of definite implication preferably compound be that E is monobasic or unsubstituted phenyl, thiadiazolyl group or pyridyl, particularly E are phenyl, cyano-phenyl, nitrophenyl, chlorophenyl, the fluoro phenyl, aminomethyl phenyl, tert-butyl-phenyl, p-methoxy-phenyl, trifluoromethyl, methyl thiazolium di azoly, pyridyl, the chloro-pyridine base, the compound of 5-flumethiazine base or chloro 5-flumethiazine base.
Be f from subunit group) in those compounds of definite implication preferably compound be that D is-O-CH 2Compound.
Be f from subunit group) in those compounds of definite implication preferably compound be that D is the compound of oxygen.
Be f from subunit group) in those compounds of definite implication preferably compound be that D is the compound of oxygen.
Be f from subunit group) in those compounds of definite implication preferably compound be D be oxygen or-O-CH 2, Y is that fluorine and Z are hydrogen, particularly D be oxygen or-O-CH 2-, Y is a fluorine, Z is that hydrogen and n are 0, especially D be oxygen or-O-CH 2-, Y is a fluorine, and Z is a hydrogen, and n is that O and B are the compounds of an ethylene bridge.
Be f from subunit group) in those compounds of definite implication preferably compound be that E is a phenyl, cyano-phenyl, nitrophenyl, chlorophenyl, fluoro phenyl, aminomethyl phenyl, tert-butyl-phenyl, p-methoxy-phenyl, trifluoromethyl, methyl thiazolium di azoly, pyridyl, chloro-pyridine base, 5-flumethiazine base or chloro 5-flumethiazine base, particularly D be on the one hand oxygen or, be on the other hand-O-CH 2The compound of-Ji.
Especially the compound shown in the particularly preferred formula 1 is that A is an oxygen, and B is an ethylene bridge, n be the numeral 0, D is an oxygen, sulphur or-O-CH 2-, E is a phenyl, pyridyl, and thiadiazolyl group is selected from by 1 or 2 and contains cyano group, nitro, halogen, C 1-C 4-alkyl and C 1-C 4The phenyl that-haloalkyl substituting group replaces is selected from by 1 or 2 and contains halogen, C 1-C 4-alkyl and halo-C 1-C 4The pyridyl that-alkyl substituent replaces, or C 1-C 4-alkyl thiazolyl, m are numerals 0,1 or 4, and Y is that fluorine and Z are the compounds of hydrogen.
From the compound shown in those preferred formulas 1, in formula or A be oxygen, B is
Ethylene bridge, D is an oxygen, sulphur or-O-CH 2-, m is a numeral 0,1 or 4, and n is a numeral 0, and Y is that fluorine and Z are hydrogen; Or A is-NH-in the formula, and B is an ethylene bridge, and D is oxygen or sulphur, and m is a numeral 0,1 or 4, and n is a numeral 0, and Y is that fluorine and Z are hydrogen, and these compounds are because its good activity and tool characteristic.
Be preferably according to some the individualized compounds shown in the formula 1 of the present invention below:
4,4-two fluoro-3-butenoic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
4,4-two fluoro-3-butenoic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
4,4-two fluoro-3-butenoic acid 2-(4-(4-methyl benzyloxy) phenoxy group) ethyl ester,
6,6-two fluoro-5-hexenoic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
6,6-two fluoro-5-hexenoic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
8,8-two fluoro-7-octylenic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
8,8-two fluoro-7-octylenic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
10,10-two fluoro-9-decylenic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
10,10-two fluoro-9-decylenic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
12,12-two fluoro-11-lauric acid 2-(4-phenoxy group phenoxy group) ethyl esters and
12,12-two fluoro-11-dodecylene acid esters 2-(4-benzyloxy phenoxy group)
The preparation method of compound shown in the formula 1 that the invention still further relates to free form or exist with the form of salt when needing, it for example comprises,
(a) compound shown in a compound shown in the formula (II) and the formula (III) or when suitable and the salt shown in the formula III be with or without that inert solvent exists and acid binding agent in the presence of react
Figure C9310784700161
X in formula II, Y, Z and m are that halogen is a chlorine or bromine as determined implication in formula I,
Figure C9310784700162
A in formula III, B, L, D, E and n have determined implication in formula I, or
B) compound shown in compound shown in formula V and the formula III or when needing and the salt shown in the formula III react being with or without under the situation that an inert solvent, catalyzer or dewatering agent exist
Figure C9310784700171
X in formula V, Y, Z and m are as determined implication in formula I,
In each case, if desired, free cpds shown in the formula I for preparing by present method a salt can be changed into, perhaps the salt of compound shown in the formula I for preparing by present method free cpds or the different salt shown in the accepted way of doing sth I can be transformed.
Method reaction a) is not preferably carried out in the inert solvent of hydroxyl in the presence of organic bases, pyridine 4-dimethylaminopyridine for example, lutidine, Alpha-Methyl-4-ethylpyridine, trialkylamine, N, the N-dialkyl aniline, or dicyclo, non-nucleophilic alkali is as 1,4-diazabicyclo (2.2.2) octane (DABCO), 1,5-diazabicyclo (4,3,0)-and 5-nonene (DBN) or 1,8-diazabicyclo (5,4,0)-and the 7-undecylene (1,5-5) (DBU).Usually, be reflected under-30 ° to+70 ° and carry out, preferred-10 ℃ to+50 ℃.Reaction is preferably in reaction is in inert solvent or the mixed solvent to be carried out.Being suitable for this purpose solvent is, for example aliphatics or aromatic hydrocarbon based benzene,toluene,xylene, sherwood oil or hexane; Halogenated hydrocarbon such as chlorinated benzene, methylene dichloride, ethylene dichloride, chloroform or tetracol phenixin, zellon; Ether and class ether compound such as dialkyl ether (ether, diisopropyl ether, t-butyl methyl ether etc.), methyl-phenoxide, dioxan, tetrahydrofuran (THF); Nitrile such as acetonitrile or propionitrile; Ester class such as ethyl acetate, propyl acetate or butylacetate; Ketone such as acetone, diethyl ketone, methylethylketone; The mixture mutual as these solvents.In addition, reaction also can be carried out under the situation of excessive alkali recited above, or the compound shown in the formula III is under the situation of an amine (A=NR1), and second normal or a large amount of excessive formula III compound also can be used to alternate base.Reaction is to carry out under normal pressure, even also can carry out under pressurization or decompression.
At method b) in, reaction is preferably in the esterification the conventional dewatering agent that uses to be carried out under existing, and for example reacts having in the presence of carbodiimide (dicyclohexyl base carbodiimide (DCC)) or 1-alkyl-2-haloperidid salt such as the 1-methyl-2-chloro-pyridine hydriodate.Being reflected at-30 ℃ to 70 ℃ preferred-10 ℃ to+50 ℃ reaches reaction is and carries out in inert solvent or the solvent mixture to good.Reaction is preferably in alkali, for example
Organic bases, as trialkylamine (Trimethylamine, triethylamine, tripropylamine or diisopropyl ethyl amine), pyridines (as 4-dimethylaminopyridine or 4-pyrrolidyl pyridine),
Morpholine class (N-methylmorpholine) or dialkyl benzene amine (N, accelerine or N-methyl-N-ethylaniline) carry out under existing.Suitable solvent is aliphatic hydrocarbon or aromatic hydrocarbon, benzene for example, toluene, dimethylbenzene, sherwood oil or hexane; Halogenated hydrocarbon such as chlorinated benzene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin or zellon; Ether and class ether compound such as dialkyl ether (ether, Di Iso Propyl Ether, t-butyl methyl ether etc.), methyl-phenoxide ， diox or tetrahydrofuran (THF); Nitrile such as acetonitrile or propionitrile; Ester class such as ethyl acetate, propyl acetate or butylacetate; And the mutual mixture of these solvents.
If the formula III compound is an alcohol (A=O), method b so) also can in the presence of an acidic catalyst, carry out H for example 2SO 4, HCl or sulfonic acid such as methylsulfonic acid or tosic acid.Help the carrying out that react with the alcohol shown in the excessive formula III.The water that discharges in reaction process can be removed from reaction mixture continuously.The azeotropic mixture that the conventional method of using is solvent distillation and water is removed reaction product water.The solvent that is suitable for reaching this purpose is benzene, toluene, dimethylbenzene, methylene dichloride or chloroform.
Method with routine can transform salify to the free Compound I, and salt is changed into free Compound I or other salt, for example passes through with acid treatment free cpds I, or uses alkaline purification salt.
Usually the various derivatives shown in the formula I can be obtained by shifting esterification or amidate action by the lower alkyl esters of the ω that is easy to get shown in the formula V-vinyl halides alkanoic acid.
For example, the derivative of the ester type shown in the formula I (A=O or S) can by the alcohol shown in lower alkyl esters shown in the formula Va and the formula III a or mercaptan by alkali-or acid catalysis shift esterification and obtain.
Figure C9310784700191
X in formula Va, Y, Z and m are as determined implication in formula I
Figure C9310784700201
B, D, E, L and n are as determined implication in formula I in formula III a, and A is oxygen or sulphur.
Specially suitable an acidic catalyst is HCl, H 2SO 4Or sulfonic acid.Shifting the preferred alkali of esterification for base catalysis is the sodium alkoxide or the potassium alcoholate of the pure and mild mercaptan shown in the formula III a, and it is easy to obtain from IIIa, for example by obtaining to IIIa adding sodium hydride or potassium hydride KH.Shift esterification preferably-20 ℃ and+carry out between 120 ℃, particularly 0 ℃ and+100 ℃ between.Use shown in the excessive formula III a alcohol or to reacting favourable.Suitable solvent is ethers such as ether, Di Iso Propyl Ether, dioxan or tetrahydrofuran (THF), halogenated hydrocarbon or aliphatics or aromatic hydrocarbon based.
Amide derivatives (A=NR shown in the formula I 1) can be by amine shown in lower alkyl esters shown in the formula Va and the formula III b or the preparation of its reactant salt
Figure C9310784700211
R in formula III b 1, B, D, E, L and n are as determined implication in formula I.Amidate action 0 ℃ and+carry out between 120 ℃.Reactant is preferably in inert solvent or the inert solvent mixture and reacts.These solvents for example are, aliphatics and aromatic hydrocarbon based as benzene, toluene, dimethylbenzene, sherwood oil or hexane; Halogenated hydrocarbon such as chlorinated benzene, methylene dichloride, Ethylene Dichloride, chloroform, tetracol phenixin or zellon; Ethers and ether compound such as dialkyl ether (ether, Di Iso Propyl Ether, t-butyl methyl ether etc.), methyl-phenoxide, dioxan or tetrahydrofuran (THF); Nitrile such as acetonitrile or propionitrile; Alcohols such as methyl alcohol, ethanol, propyl alcohol or Virahol; Or water.Use the amine shown in the excessive formula III b to reacting favourable.
Formula II, III, IIIa, IIIb, compound shown in V and the Va and preparation thereof can be known from document.Formula II and or V shown in compound can prepare by the method described in US-4950666 and the EP-A-0432861.Prepared free acid and subsequently the acid shown in this formula V is transformed arbitrarily the carboxylic acid halides shown in the accepted way of doing sth II by ester, its reaction conditions accords with acid-or alkali catalyzed hydrolysis, or the popular response condition of carboxylic acid halogenating reaction.The formula III that does not appear in the newspapers in these former documents, the compound shown in IIIa and the IIIb can obtain with the currently known methods that is similar to conventional synthetic method.
Z be shown in the formula I of hydrogen or methyl the compound with the form of free form or salt can also prepare in the following method, promptly use the ω shown in the formula (IV)-carbonyl alkanoic acid derivs, or can be with its salt and methyl halide such as CF when needing 2Br 2, CCl 2F 2Or CCl 3F, or alkaline three halogenated acetic acids salt such as ClF 2C-CO-ONa or CCl 2F 2-CO-ONa is in inert solvent and at trisubstituted phosphine such as P (C 6H 5) 3, P (C 2H 5) 3, P (N (C 2H 5) 2) 3Or P (N (CH 3) 2) 3React under existing
A in formula (IV), B, L, D, E, m and n are as determined implication in formula I.
The solvent that is particularly suitable for this reaction is ethers such as diglyme, triglyme or tetraethylene glycol dimethyl ether, or N,N-DIMETHYLACETAMIDE.Usually this step reaction be 0 ℃ and+carry out between 150 ℃, preferred+20 ℃ and+100 ℃ between.
Compound shown in the formula IV and its salt are new compounds.They are specially to develop for the effective constituent shown in the synthesis type I.So the compound shown in the formula IV also is a part of the present invention.
The raw material that compound shown in the formula IV can maybe can be buied by the raw material of having recorded and narrated in the document is by in fact known method preparation.For example, but acid or carboxylic acid halides shown in the preparation through type VI of compound shown in the formula IV or also available its salt when needing, in inert solvent and have in the presence of catalyzer or the dewatering agent and react with compound shown in the formula III
M is as determined implication in formula I in formula VI, and G is hydroxyl or halogen, preferred chlorine or bromine, and Z is hydrogen or methyl.The reaction conditions of this esterification or amidate action meet method a) and b) in reaction conditions.
Compound shown in the formula VI is known or available and the similar method preparation of currently known methods.
Compound with more specific subunit group or its salt shown in the formula IVa can also prepare in the following method, promptly by calorifying shown in the formula VII in the methyl-sulphoxide
ω halogenated alkane carboxylic acid derivative or its salt.Temperature of reaction preferably+50 ℃ and+180 ℃ between.
Figure C9310784700232
A in formula IVa, B, D, E, L, m and n are as determined implication in formula I,
Figure C9310784700241
A in formula VII, B, D, E, L, m and n are that halogen is a chlorine, bromine or iodine as determined implication in formula I.
Compound shown in the formula VII can be with being similar to a) and b) esterification or amidation by the compound shown in the formula VIII
Hal-CH 2-CH 2-(CH 2-CH 2) m-CO-G (VIII)，
M is that G is hydroxyl or halogen as determined implication in formula I just in formula VIII, preferred chlorine or bromine, and Hal is a chlorine, bromine or iodine.
Compound shown in the formula VIII is the known or available known method preparation that is similar to.
Y is that the formula I compound of chlorine can exist with the double bond isomer form of E formula and Z formula.Can from isomer mixture, isolate pure double bond isomer by means of physical method as distillation or solid-liquid chromatogram.
According to Compound I of the present invention is effective constituent useful in the PCO field, simultaneously can be by homoiothermy class animal, and fish and plant are born.Effective constituent of the present invention is tasted in the plant for useful plant and sight on agricultural and the gardening, paddy rice particularly, cotton, insect of finding in these farm crop of fruit and vegetables and the forest and spider biologically active.Formula I compound is particularly suitable for preventing and treating paddy rice, and the insect on these farm crop of fruit tree and vegetables particularly endangers insect such as bean aphid, Nilaparvata lugen (brown planthopper) and the rice green leafhopper of plant.According to the application of effective constituent of the present invention in other field is the product and the goods and materials of protection storage, and the health aspect, particularly protects livestock and poultry.
Compound I also has each etap of resistant strain insect that biological activity is all arranged for common sensitive strain.Their biological activity is very significant, and they can be immediately or be further along as insect is destroyed, or reduce product and/or the hatching rate of insect.
Insect recited above comprises:
Lepidopteran, for example
Acleris spp belongs to several, and Adoxophyes spp belongs to several, and clearwing moth belongs to several, Agrotis several, cotton leaf ripple noctuid, Amylois spp., Anticarsia, Archips spp several, Argyrotaenia spp belongs to several, Noctua several, corn pattern noctuid, meal moth, peach fruit moth, snout moth's larva belongs to several, and the look volume belongs to several, grape codling moth (Clysia ambiguella), the leaf roll snout moth's larva belongs to several, and the volume moth belongs to several, Cochylisspp belongs to, and sheath worm moth belongs to several, Crocidolomia binotalis, Cryptophlebia leucotreta, leaf roller belongs to several, and Pyrausta nubilalis (Hubern). belongs to several, Diparopsis castanea, Earias several, the powder snout moth's larva belongs to several, the flower steinernema belong to several, ligustrum fine tortricidae, Euproctis several, cutworm belongs to several, and heart-eating worm belongs to several, wide wing steinernema, Noctua several, Oeobia undalis, fall webworms, the moth-eaten moth of tomato, apple leaf-miner, thin moth belongs to several, flower wing steinernema, Euproctis several, leaf miner belongs to several, Malacosoma several, lopper worm, maduca sexta, looper belongs to several, European corn borer, super steinernema belongs to several, and leaf roller belongs to several, small noctuid, pink bollworm, phthorimaea operculella, small white, Pier several, small cabbage moth, Yponomeuta several, white wild snout moth's larva belongs to several, pink rice borer belongs to several leaf rollers and belongs to several, mythimna separata belongs to several, and clearwing moth belongs to several, and the band moth belongs to several, the volume moth belong to several, cabbage looper and the tree ermine moth several;
Coleoptera, for example
Click beetle belongs to several, and weevil belongs to several, and Atomaria linearis, Chaetocnema tibialis, grain weevil belong to several, and weevil belongs to several, khapra beetle belongs to several, chrysomelid genus several, ladybug belongs to several, Eremus spp., colorado potato bug, Lissorhoptrus oryzophilus Kuschel belongs to several, metal several, ostomatid belongs to several, ear resembles and belongs to several, phlyctinus spp., Japanese beetle, phyllotreta several, moth-eaten belong to several, chafer, Sitophilus several, gelechiid belongs to several, powder genus beacon kind, and several belong to several with the spot khapra beetle Tribolium;
Orthoptera, for example
Figure C9310784700261
Lian belongs to several, and Lian belongs to several, Gryllotalpa spp several, Ma Dela
Figure C9310784700262
Lian, migratory locusts belong to several, and several belong to several with grasshopper Periplaneta;
Isoptera, for example
Cryptotermes several,
Corrodentia, for example:
Booklice belongs to several;
Anoplura, for example
Blind lice belongs to several, and the jaw lice belongs to several, Cuclotogaster several, the goitre cotten aphid belong to several and Phylloxera spp several;
Mallophaga, for example raise lice and Trichodectes several;
Thysanoptera, for example
Thrips several, Hercinothrips spp belongs to several, careless Thrips several, pale brown thrips, cotton thrips comes Scirtothrips aurantii;
Heteroptera, for example
Cimex several, Distantiella theobroma, red stinkbug belongs to several, Euchistus spp., brown scutteleerid belongs to several, Leptocorisa spp belongs to several, Nezara viridula smaragdula Fabricius. belongs to several, intend lace bug and belong to several, red pig stinkbug, Sahlbergella singularis, black stinkbug belong to several and suction and blood Reduvius several;
Homoptera, for example
Wolly whitefly, the wild cabbage aleyrodid, the red a red-spotted lizard of circle belongs to several, Aphidiadae, Aphis several, the circle a red-spotted lizard belong to several, sweet potato whitefly, lecanium belongs to several, Chrysomphalus aonidium, dictyospermum scale, Coccushesperidum, Empoasca spp belongs to several, apple aphid, the spot cicada belongs to several, gummy a red-spotted lizard, the rice small brown rice planthopper belongs to several, brown grey lecanium, and lepidosaphes belongs to several, the pipe Aphis several, tumor aphid genus several, rice green leafhopper belongs to several, brown back rice plant hopper belongs to several, paratoria spp., and the knurl woolly aphid belongs to several, citrus mealy bug belongs to several, and white peach scale belongs to several, and mealybug belongs to several, several cotton a red-spotted lizards circle a red-spotted lizards of Psylla spp belong to several, Rhopalosiphum several, the helmet a red-spotted lizard belongs to several, leafhopper belongs to several, the y-bend Aphis several, the long tube stinkbug, Trialeurodes vaporariorum Westwood, an African mandarin orange and tangerine wood louse Unaspis citri;
Hymenoptera, for example
Acromyrnex, leaf cutting ant belongs to several, European wheat stem sawfly belongs to several, Diprionidae, Gilpinia polytoma, real tenthredinidae several, the field ant belongs to several, the kitchen ant, Neodiprion spp belongs to several, Solenopsis several and Vespa several;
Diptera, for example
Aedes several, Antherigona soccata, march fly, calliphora erythrocephala, Anastrepha several, Drosophila several, Culex several, cuterbrid belongs to several, Anastrepha several, yellow raw meat raw meat fruit bat, fly belongs to several, the stomach fly, Glossina several, bomb fly belongs to several, hippoboscid, Hippelates several, lucilia sericata belongs to several, Liriomyza belongs to several, Musca several, the nose fly belongs to several, the standing grain cecidomyiia, auspicious bent wheat stem chloropid fly, spinach leaf mining flowerfly, Anthomyia several, Rhagoletis pomonella, point eye uranotaenia, Stomoxys, Gadfly several, night, cicada belonged to, big uranotaenia several;
Siphonaptera, for example
The leaf flea belongs to several, India visitor flea;
Thysanura, for example
Silverfiss;
Acarina, for example
Acarus siro, tangerine bud goitre mite, apple thorn goitre mite, Amblyomma several, sharp tick belongs to several, Boophilus several, short whisker Acarapis several, Bryobia praetiosa, last three the joint Eriophyeses several, Psoroptes several, cock skin thorn tick, carpinus turczaninowii beginning tetranychid, tea Fischer Eriophyes several, Hyalomma several, hard tick belongs to several, meadow unguiculus mite, prominent Ornithodoros several, Panonychus citri belongs to several, sweet tangerine rust mite, side is eaten the tree line mite more, and the scabies mite belongs to several, Rh several, the root mite belongs to several, and itch mite belongs to several, tarsonemid mite belong to several and Tetranychus several.
Compound shown in the formula I is particularly suitable for preventing and treating cotton, vegetables, the harmful organism on these farm crop of fruit tree and paddy rice such as the mite class on the paddy rice, aphid, caterpillar, plant and leaf springtail.The primary pest mite class that can prevent and treat as panonychus ulmi, Phytophthira such as bean aphid, caterpillar such as cigarette bud are looked plant one on noctuid and the paddy rice and leaf springtail such as Nilaparvata lugen (brown planthopper) or black secret genus leaf tick.
Then be equivalent to the lethality rate of above-mentioned insect is at least 50-60% according to its good pesticide activity of Compound I of the present invention.
According to Compound I of the present invention with contain their composition, can strengthen its field of activity greatly and can use in a lot of occasions by adding other sterilant and/or miticide.Below several classes composition representative is effectively arranged is example as suitable additive: organo phosphorous compounds, nitropheneol and derivative thereof, formamidine, ureas, amino formate, pyrethroid, chlorinated hydrocarbon and Bacillus thuringiensis prepared product.
Compound shown in the formula I can use its pure effective constituent or best auxiliary agent commonly used in some complete processings to use, their available known methods for example are processed into, missible oil, solution that can directly spray or dilutable, dilute emulsion, wettable powder, soluble powder, pulvis, granule also has the capsule in polymkeric substance.Using method for example has sprays, and atomizing is dusted, and broadcasts sowing or bold and vigorous watering, and composition can also selectedly make its target that is suitable for being scheduled to and concrete environment place.
These preparations that contain effective constituent shown in the formula I that have or do not have solid or fluid additive are composition, prepared product or mixture, or these effective constituents and other sterilant or acaricidal mixture can be with known method processing and preparing, for example with effective constituent and spreading agent, as solvent, solid carrier also has tensio-active agent thoroughly to mix together in case of necessity, and/or grinds.
The solvent that is fit to is as follows: arene, preferred C 8-C 12Alkyl benzene such as xylene mixture or alkylated naphthalene, aliphatics or alicyclic hydro carbons such as hexanaphthene, paraffin or naphthane, alcohols such as ethanol, propyl alcohol or butanols and glycols and their ether and ester are as propylene glycol, dipropylene glycol, ethylene glycol, glycol monomethyl methyl ether or ethylene glycol monomethyl ether, ketone such as pimelinketone, isophorone or diacetyl alcohol, intensive polar solvent such as N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO) or dimethyl formamide, or water, vegetables oil such as rapeseed oil, Viscotrol C, Oleum Cocois or soya-bean oil; If suitable, also available silicone oil.
Used solid carrier is such as common with natural ground mineral substance such as calcite, talcum, kaolin, polynite or atlapulgite to pulvis and dispersible pulvis.In order to improve physicals, also can add the silica or the high dispersive adsorbability polymer of polymolecularity.It is possible microgranular that granule is used, adsorptive support or porous types of materials as float stone, the brickbat grain, sepiolite or saponite, or non-adsorptive support material are as calcite or sand.A large amount of in addition granular inorganic or organic substances also can use, for example particularly rhombspar or comminuted plants residue.
Be processed into the character of effective constituent shown in the formula I of preparation or these effective constituent and other sterilant or miticide mixture according to need, the used tensio-active agent that is fit to is that those have fine emulsification, the non-ionic type of dispersion and wettability, cationic and/or anion surfactant.Tensio-active agent also can be regarded as surfactant mixtures.
Suitable anion surfactant can be water miscible soap or water miscible synthetic surface active cpd.
Suitable soap is an alkali metal salt, the unsubstituted higher fatty acid (C of alkaline earth salt or replacement 10-C 22) ammonium salt such as the sodium salt or the sylvite of oleic acid or stearic sodium salt or sylvite, the natural acid mixture that maybe can from Oleum Cocois or Yatall MA, obtain.Other tensio-active agent refers to the fatty acid methyl taurate.
But, usefulness more be the tensio-active agent of so-called synthetic, particularly aliphatic sulfonate, aliphatic sulphate, sulphonated benzimidazole derivative or alkylaryl sulphonate.
Aliphatic sulfonate or aliphatic sulphate normally are an alkali metal salt; ammonium salts alkaline earth salt or replacement or unsubstituted also has an alkyl that contains 8 to 22 carbon atoms usually; alkyl also comprises the moieties of carboxyl groups; lignosulfonic acid for example, laurilsulfate or by the sodium salt or the calcium salt of the fatty alcohol sulphuric acid ester mixture of natural acid preparation.This group also comprises the salt/ethylene oxide adduct of sulfuric ester and Fatty Alcohol(C12-C14 and C12-C18) sulfonic acid.Sulphonated benzimidazole derivative preferably contains 2 alkylsulfonyls and a compound that contains the fatty acid group of about 8-22 carbon atom.Alkylaryl sulphonate is a Witco 1298 Soft Acid for example, sodium salt, calcium salt or the triethanolamine salt of a dibutyl naphthene sulfonic acid or a naphthene sulfonic acid/formaldehyde condensation products.Suitable phosphoric acid salt is that salt/(4-14) ethylene oxide adduct, or phosphatide of a for example contraposition nonyl phenol phosphate also is suitable.
Suitable nonionogenic tenside mainly is aliphatics or alicyclic alcohol, the polyglycol ether derivative of saturated or unsaturated lipid acid and alkylphenol, they contain 3 to 30 ethylene glycol ether groups and partly contain 8 to 20 carbon atoms at aliphatic hydrocarbyl, contain 6 to 18 carbon atoms in the alkyl group of alkylphenol.Other suitable nonionogenic tenside is water miscible polyethylene oxide and contain 1 to 10 carbon atom and contain the polypropylene glycol of 20 to 250 ethylene glycol ethers and 10-100 propylene glycol ether, the affixture of ethylene diamino polypropylene glycol and alkyl polypropylene glycol in alkyl chain.Contain 1 to 5 ethylene glycol unit in each propylene glycol unit of above-claimed cpd.
Examples of nonionic surfactants is the nonyl phenol polyethoxyethanols, Viscotrol C polyglycol ether, poly(propylene oxide)/polyethylene oxide affixture, tributyl phenoxy group polyethoxyethanols, polyoxyethylene glycol and octylphenoxy polyethoxy ethanol.The fatty acid ester of polyoxyethylene sorbitol acid anhydride also is suitable nonionic surface active agent as polyoxyethylene sorbitol acid anhydride oleic acid ester.
Cats product mainly is a quaternary ammonium salt, replaces other as N and contains a alkyl group at least with 8 to 22 carbon atoms, and be rudimentary as other substituting group, halogenated or not halogenated alkyl, benzyl or rudimentary hydroxyalkyl group.Salt is preferably with halogenide, the salt of Methylsulfate or ethylsulfuric acid salt form, for example stearyl-trimethyl ammonium chloride or benzyl two-(2-chloroethyl) ethyl brometo de amonio.
Tensio-active agent recited above only is to be used as some examples; A large amount of commonly used and to be suitable for tensio-active agent of the present invention on the books in some special documents in formulation processing.
Usually, pesticide preparation contains 0.1-99%, particularly the effective constituent I of 0.1-95% or this effective constituent and other sterilant and/or miticide, and 1-99.9%, particularly 5-99.9% a solid or a liquid adjuvants, usually, the tensio-active agent (% refers to weight percent) that contains 0.-25%, particularly 0.1-25% in the preparation.And commodity preferably are prepared into the form of enriched material, and last user uses the quite low dilution formulation of effective constituent concentration usually.Typical working concentration be 0.1 and 1000ppm between, preferred 0.1 and 500ppm between.The per hectare consumption is generally 1-1000g effective constituent, preferred 25-500g/ha.
Preferred formulation its (%=weight percent) composed as follows:
Missible oil:
Effective constituent: 1-90%, preferred 5-20%
Tensio-active agent: 1-30%, preferred 10-20%
Liquid vehicle: 5-94%, preferred 70-85%
Pulvis:
Effective constituent: 0.1-10%, preferred 0.1-1%
Solid carrier: 99.9-90%, preferred 99.9-99%
Suspending concentrate:
Effective constituent: 5-75%, preferred 10-50%
Water: 94-24%, preferred 88-30%
Tensio-active agent: 1-40%, preferred 2-30%
Wettable powder:
Effective constituent: 0.5-90%, preferred 1-80%
Tensio-active agent: 0.5-20%, preferred 1-15%
Solid carrier: 5-95%, preferred 15-90%
Granule:
Effective constituent: 0.5-30%, preferred 3-15%
Solid carrier: 99.5-70%, preferred 97-85%
Preparation can also contain other auxiliary material such as the epoxidation of stablizer class or non-epoxidised vegetables oil (as the epoxidation Oleum Cocois, rapeseed oil or soya-bean oil), the defoamer class as silicone oil, sanitas, viscosity modifier, binding agent and/or tackifier also can contain fertilizer or in order to obtain the effective constituent that special effect also can contain other.
Following Example but is not limited to this in order to explanation the present invention.Temperature is with centigrade thermometer.
Preparation example
Example H1:2-(4-phenoxy group phenoxy group) ethyl 4,4-two fluoro-3-crotonates (table 1, compound N are o.1.01)
Contain 3.0g 4, the 50ml diethyl ether solution of 4-two fluoro-3-butenoic acids 0.36g4-pyrrolidyl pyridine and 5.66g 2-(4-phenoxy group-phenoxy group) Ethanol Treatment, mixture is cooled to 0 ℃.0 ℃ and+be the N of 5.58g between 5 ℃ with total amount, N '-dicyclohexylcarbodiimide adds several times, removes ice-cooled device, allows reaction mixture in stirring down, reaches room temperature in 16 hours.Separation also discards solid sediment N, N '-dicyclohexylurea (DCU).The evaporation supernatant liquor.Residue silica gel column chromatography (eluent, hexane/ethyl acetate, 9: 1) purifying.Obtain the pure 2-of buttery (4-phenoxy group phenoxy group) ethyl 4,4-two fluoro-3-crotonate (refractive index ns D 23: 1.5315).
Example H2: but the preparation of the method described in other compound use-case H1 shown in the cited formula 1 among the following table 1-6.In " physical parameter " hurdle of these tables, " m.p. " represents the fusing point of the compound of studying, " n D TThe specific refractory power of the compound studied of representative when temperature T ℃.Table 1
Figure C9310784700361
Table 1 (continuing)
Figure C9310784700371
Table 1 (continuing)
Figure C9310784700381
Table 2Table 2:
Figure C9310784700391
Figure C9310784700392
Table 2 (continuing)
Figure C9310784700401
Table 2 (continuing)
Figure C9310784700411
Table 2 (continuing)
Figure C9310784700421
Table 3
Figure C9310784700422
Figure C9310784700423
Table 3 (continuing)
Figure C9310784700431
Table 3 (continuing)
Figure C9310784700441
Table 4
Figure C9310784700452
Table 4 (continuing)
Figure C9310784700461
Table 4 (continuing) Table 5
Figure C9310784700481
Table 5 (continuing) Table 5 (continuing) Table 5 (continuing)
Figure C9310784700511
Table 6
Figure C9310784700521
Figure C9310784700522
Table 6 (continuing)
Figure C9310784700531
The formulation preparation example, (% is weight percentage) routine F1: missible oil is b a)) c) active ingredient No.1.01 25% 40% 50% calcium dodecyl benzene sulfonates 5% 8% 6% castor oil polyglycol ether 5%--, (EO of 36mol) tributyl phenol polyglycol ether, (EO of 30mol)-12% 4% cyclohexanone-15% 20% xylene mixture 65% 25% 20% these concentrated milk oils of dilute with water can obtain any emulsion that needs concentration. Example F2:solution is b is a)) c) d) effective constituent No.1.01 80% 10% 5% 95% second diether monomethyl ether 20%---polyoxyethylene glycol, (molecular weight 400)-7%--N-N-methyl-2-2-pyrrolidone N--20%--epoxidation Oleum Cocois--1% 5% gasoline, (160-190 ℃ of boiling spread)--94%-
This solution is suitable for using with little drop form.
Example F3: granule is b a)) c) d)
Effective constituent No.1.01 5% 10% 8% 21%
Kaolin 94%-79% 54%
Polymolecularity silica 1%-13 7%
Atlapulgite-90%-18%
Effective constituent is dissolved in the methylene dichloride, and solution is sprayed on the carrier, and that continues boils off solvent under vacuum.
Example F4: pulvis is b a))
Effective constituent No.1.01 2% 5%
Polymolecularity silica 1% 5%
Talcum 97%-
Kaolin-90%
Carrier thoroughly mixed with effective constituent obtain the finished product pulvis.
Example F5: wettable powder is b a)) c)
Effective constituent No.5.01 25% 50% 75%
Sodium lignosulfonate 5% 5%-
Sodium Lauryl Sulphate BP/USP 3%-5%
Diisobutyl sodium naphthalene sulfonate-6% 10%
Octyl phenol polyglycol ether
(EO of 7-8mol)-2%-
Polymolecularity silica 5% 10% 10%
Kaolin 62% 27% 1
Effective constituent and additives mixed and in a suitable mill length grind.The wettable powder that obtains with this method can be diluted with water to any suspension that needs concentration.
Example F6: missible oil
Effective constituent No.5.01 10%
Octyl phenol polyglycol ether 3%
(EO of 4-5mol)
Calcium dodecylbenzene sulphonate 3%
Viscotrol C polyglycol ether 4%
(EO of 36mol)
Pimelinketone 30%
Xylene mixture 50%
This concentrated milk oil of dilute with water can obtain any emulsion that needs concentration.
Example F7: pulvis: a) b)
Effective constituent No.5.01 5% 8%
Talcum 95%-
Kaolin-92%
Effective constituent and carrier mixed to be incorporated in to grind in the suitable mill can obtain the finished product pulvis.
Example F8: extruding granule
Effective constituent No.5.01 10%
Sodium lignosulfonate 2%
Carboxymethyl cellulose 1%
Kaolin 87%
Effective constituent and additives mixed, mixture are ground, and also water is moistening.With the extruding of this mixture, granulation, continue at air drying.
Example F9: coated granule
Effective constituent No.5.01 3%
Polyoxyethylene glycol (molecular weight 200) 3%
Kaolin 94%
In a mixing tank, the effective constituent of grinding very carefully evenly is added to the wetting kaolin surface of polyoxyethylene glycol.Can obtain non-dusting coated granule in this way.
Example F10: suspending concentrate
Effective constituent No.5.01 40%
Ethylene glycol 10%
Nonyl phenol polyglycol ether 6%
(EO of 15mol)
Sodium lignosulfonate 10%
Carboxymethyl cellulose 1%
The silicone oil 1% of 75% water miscible liquid form
Water 32%
Ground effective constituent is thoroughly mixed with additive.The suspending concentrate dilutable water that obtains thus becomes any suspension that needs concentration.Biological Examples
Example B1: to the activity of boophilus microplus: suck full female one-tenth tick and be placed on the PVC plate, cover with cotton balls.With 10ml effective constituent concentration is that the aqueous solution of the reagent agent of 125ppm is poured into and handled the examination worm on the plate.Remove cotton balls then, the examination worm is incubated 4 Zhou Rangqi and lays eggs.Medicament can be represented with the lethality rate sterility female worm the activity of boophilus microplus, for ovum; Available ovicidal activity is represented.In this test, the table 1-6 compound exhibits good activity.Particularly be numbered 1.01,2.01 to 2.06,2.10,2.12,2.14 to 2.16,2.20,2.22,2.23,2.26,3.01,4.01,4.02,4.05,4.06,4.20,5.01 to 5.03,5.05, its activity of 5.06 and 5.20 to 5.25 compound is more than 80%.
Example B2: to the activity of Nilaparvata lugen (brown planthopper).
Spray the treating water rice plants with the water emulsion mixture that contains 400ppm effective constituent.After treating that the topped soup in plant surface is done, on plant, draw and connect the 2-3 brown lice larva of rice in age.21 days postevaluation test-results.Determine the per-cent (% activity) that examination worm colony reduces by the quantity that survives the examination worm on the comparison process plant and the plant of being untreated.In this test, the compound exhibits of table 1-6 has gone out good activity.Particularly be numbered 1.01,2.01 to 2.03,2.07,2.08,2.10 to 2.16,2.20,2.22,2.23,2.26,3.01,4.01 to 4.06,4.20,5.01 to 5.06,5.08,5.10 to 5.12,5.15, its activity of 5.16 and 5.20 to 5.25 compound is more than 80%.
Example B3: to the activity of Ctenocephalides felis
In the 50ml of horizontal positioned tissue culture flasks, put in advance and place 20 to 25 flea ovum again after 15g contains the larva nutrient media that confession examination effective constituent concentration is 100ppm.Then bottle is placed temperature 26-27 ℃, in the brooder of relative humidity 60-70%.After 21 days, check to become flea, the number of pupa and larva in the bottle.
In this test, the compound exhibits among the table 1-6 has gone out good activity, particularly is numbered 1.01,2.02 to 2.08,2.10 to 2.15,2.22,2.23,2.26,3.01,4.03, and its activity of 4.04,5.08 and 5.10 to 5.12 compound is more than 80%.
Example B4: to the effect of bean aphid
Bean aphid drawn receive on the bean seedlings, it is that the spray mixing liquid of 400ppm is sprayed at 20 ℃ of insulations down that the usefulness that continues contains effective constituent concentration.3 days and 6 days postevaluation test-results.Plant pearl by comparison process and determine the per-cent (% activity) that colony reduces with the dead aphid number that is untreated on the plant.
In this test, the compound exhibits of table among the 1-6 gone out good activity, particularly numbers its activity of compound of 1.01,2.01 to 2.07,2.10 to 2.13,2.22,2.23,3.01,5.05 and 5.20 to 5.25 more than 80%.
Example V5: to the systemic activity of Nilaparvata lugen (brown planthopper)
The basin that will contain rice plant is put into the water miscible liquid that effective constituent concentration is 400ppm.The larva in special 2-3 age of continuing is drawn and receives on the rice plant.6 days postevaluation test-results.Plant pearl by comparison process and determine that with the quantity of insect that is untreated on the plant colony reduces per-cent (% activity).
In this test, the compound exhibits of table 1 in 6 good activity.Particularly be numbered 1.01,2.01 to 2.08,2.10 to 2.16,2.20,2.22,2.23,2.26,3.01,4.01 to 4.06,4.20,5.01 to 5.08,5.10 to 5.12,5.15, its activity of 5.16 and 5.20 to 5.25 compound is more than 80%.
Example B6: to the activity of panonychus ulmi (organophosphorus and carbamate chemicals for agriculture are had resistance)
On apple seedling, draw the female insect that connects panonychus ulmi.Be that the water miscible liquid of the test compound of 400ppm spray to be handled the plant of having been infected to there being drop to drip with concentration after 7 days, place the greenhouse to cultivate then.14 days postevaluation test-results.Determine the per-cent (% activity) that colony reduces by the dead mite number on the comparison process plant and the plant of being untreated.
In this test, the compound exhibits among the table 1-6 has gone out good activity, particularly is numbered 1.01,2.01,2.07,2.08,2.10,2.12 to 2.16,2.22,2.23,2.26,3.01,4.01,4.02,4.06,5.01 to 5.03,5.05,5.06,5.08,5.10,5.11 its activity of 5.15,5.16 and 5.20 to 5.25 compound is more than 89%.
Example B7: to the activity of rice green leafhopper
With containing the water emulsion mixture sprinkling treating water rice plants that effective constituent concentration is 400ppm.After the soup for the treatment of the plant surface is done, on plant, draw and connect the 2-3 rice green leafhopper larva in age.21 days postevaluation test-results.Number by survival insect on the comparison process plant and the plant of being untreated is determined the per-cent (% activity) that colony reduces.
In this test, the compound exhibits of table among the 1-6 good activity.Particularly be numbered 1.01,2.01,2.02,2.03,2.06,2.07,2.10 to 2.12,2.14 to 2.16,2.23,2.26,3.01,4.01,4.02,4.05,4.06,5.01 to 5.03,5.05,5.10 to 5.12,5.15,5.16,5.20,5.22,5.24 and 5.25 compound, its activity is more than 80%.
Example B8: to the activity of sweet potato whitefly
Place short beans plant in the standard cage and draw and connect sweet potato whitefly adult (white plant hopper).After waiting to lay eggs, remove all adults, after 10 days, with prepared containing for examination effective constituent concentration be that the water emulsion mixture of 400ppm sprays and handles the plant that is attached with nymph.14 days by its hatching percentage evaluation test result recently that compares with the contrast of not handling with effective constituent.
In this test, the compound exhibits among the table 1-6 goes out good activity, particularly is numbered 1.01,2.01 to 2.08,2.10 to 2.16,2.22,2.23,3.01,4.01,4.02,4.05,4.06,5.02,5.03,5.06 to 5.08,5.10,5.11,5.20,5.21 and 6.09 compound, its activity is more than 80%.
Example B9: to the activity of 3 tetranychids
The population mixture of 3 tetranychids drawn connect on the immature bean seedlings, spray with the water miscible liquid spraying mixture that contains effective composition 400ppm after 1 day and handle.That continues is incubated 6 natural postevaluation drug effects with plant down at 25 ℃.By comparing dead ovum on plant with the plant of being untreated, larva with become borer population to determine the per-cent (% activity) that colony reduces.
In this test, the compound exhibits of table 1 to 6 good activity.Particularly be numbered 1.01,2.01 to 2.08,2.10,2.12 to 2.16,2.22,2.23,2.26,3.01,4.01 to 4.06,4.20,5.01 to 5.06,5.08 to 5.12,5.15,5.16 and 5.20 to 5.25 compound, its activity is more than 80%.
Example B10: to the activity of Heliothis virescens.
Spray the young bean seedlings of processing with the water miscible liquid that contains effective composition 400ppm.After treating that plant surface soup is done, draw the Heliothis virescens that connects 10 1 ages on the bean seedlings, and place plastic containers.6 days postevaluation test-results.By the plant of handling with medication not compare the quantity of kemp caterpillar and situation that plant is endangered really the grouping body reduce the per-cent (% activity) that per-cent or plant harm reduce.
In this test, the compound exhibits of table 1 in 6 good activity, particularly be numbered 1.01,2.01 to 2.08,2.10 to 2.16,2.22,2.23,2.26,3.01,4.01,4.02,4.05,4.06,4.20,5.01 to 5.03 to 5.08,5.10 to 5.12,5.15,5.16,5.20 the compound to 5.22,5.24 and 5.25, its activity is more than 80%.
Example B11: to the activity of Crocidolomia binotalis Cater pillars
Spray processing Chinese cabbage seedling with the water miscible liquid spraying mixture that contains effective composition 400ppm.After treating that soup on the plant is done, on plant, draw the Crocidolomiabinotalis that connects 10 3 ages, then plant is placed plastic containers.3 days postevaluation test-results.By with untreated control comparison plant on kemp caterpillar quantity and plant like that the situation of harm determines that colony reduces the per-cent (% activity) that per-cent or plant are injured and reduce.
In this test, the compound exhibits of table among the 1-6 good activity.Particularly be numbered 1.01,3.01,5.01,5.02,5.05 and 5.20 to 5.25 compound, its activity is more than 80%.
Example B12: the activity that cotton boll is resembled adult
Spray the processing cotton seedling with the water miscible liquid spraying mixture that contains effective composition 400ppm.After treating on the plant that soup is done, draw on the Xiang Mianmiao and connect 10 cotton bolls and resemble 10 of adults, be placed on then in the plastic containers.3 days postevaluation test-results.Be subjected to the harm situation to determine the be injured per-cent (% activity) of minimizing of colony minimizing per-cent or plant by more extremely resembling number and plant with untreated control.
In this test, the compound exhibits of table among the 1-6 good activity, particularly be numbered 1.01,2.07,2.08,2.10 to 2.16,3.01,5.01,5.02,5.05,5.10,5.16 and 5.20 to 5.25 compound, its activity is more than 80%.
Example B13: to the systemic activity of black peach aphid
Black peach aphid drawn receive on the bean seedlings, the root with plant is placed in the spraying mixture that contains effective composition 400ppm then, and plant is cultivated down in 20 ℃, 3 days and 6 days postevaluation test-results.By with untreated control comparison plant on dead aphid number determine the per-cent (% activity) that colony reduces.
In this test, the compound exhibits of table among the 1-6 good activity, particularly be numbered 1.01 compound, its activity is more than 80%.
Example B14: to the systemic activity of rice green leafhopper
The basin that fills rice plant placed contain the water miscible liquid that effective composition is 400ppm.That continues draws the larva that connect for 2 and 3 ages on rice plant.Review test-results after 6 days.By with untreated control comparison plant on the quantity of leaf springtail determine the per-cent (% activity) that colony reduces.
In this test, the compound exhibits of table 1 to 6 good activity.Particularly number 1.01,2.01 to 2.06,3.01,4.01,4.02,4.06,5.01 to 5.03 and 5.24 compound, its activity is more than 80%.
Example B15: to the ovum/larvicidal activity that kills of Heliothis virescens
With containing effective composition is the cotton plants that the water miscible liquid spraying mixture spray deposition of 400ppm has the Heliothis virescens ovum.After 8 days, by with untreated control relatively the hatching per-cent and the caterpillar survival rate evaluate efficacy (per-cent that colony reduces) of ovum.
In this test, table 1 to the compound exhibits in 6 has gone out good activity, particularly is numbered 1.01,2.01 to 2.07,2.10 to 2.12,2.15,2.16,2.22,2.23,2.26,3.01,4.01 to 4.06,4.20,5.01 to 5.08,5.10 to 5.12,5.15,5.16,5.20 to 5.26 and 6.09 compound, its activity is more than 80%.
Example B16: to the activity of Dermanyssus gallinae
With 2-3ml effective constituent concentration is that the solution of 10ppm and the mite of about 200 each etap are put in our Glass Containers opened of a top.Seal container with cotton balls then, shake container 10 minutes until acarid entirely by moistening.Rotary container is so that cotton balls can be with remaining soup absorption then.After 3 days, by dead individual counting being determined the mortality ratio of acarid; Represent with per-cent.
Compound among the table 1-6 has shown good activity to Dermanyssus gallinae.Particularly number 1.01,2.06,2.13,4.01,4.02,4.04,4.05,4.06 and 5.21 compound, its activity is more than 80%.

Claims (22)

1. compound or its salt shown in the formula I who is free form,
In formula
A is an oxygen, sulphur or-NR 1-;
B is C 2-C 6-alkylidene group,
D-E is-O-E-S-E ,-O-CH 2-E ,-O-C (=O)-E ,-O-C (=O)-O-E ,-O-C (O)-N (H)-E or-O-C (=S)-N (H)-E;
E is a phenyl; Be selected from halogen, C by 1 to 3 1-C 4Alkyl, halo-C 1-C 4Alkyl, C 1-C 4Alkoxyl group, halo-C 1-C 4Alkoxyl group, cyano group, the phenyl that nitro and methylene-dioxy substituting group replace; Have 1 to 3 and be selected from nitrogen, the 5-membered aromatic heterocycle of oxygen and sulfur heteroatom; Have 1 to 3 and be selected from nitrogen, oxygen and sulfur heteroatom and be selected from halogen, C by 1 or 2 1-C 4Alkyl and C 1-C 4The 5-membered aromatic heterocycle that the haloalkyl substituting group replaces; Has 1 hexa-atomic aromatic heterocycle to individual nitrogen-atoms; Or have 1 to 3 nitrogen-atoms and be selected from halogen, C by 1 or 2 1-C 4Alkyl and C 1-C 4The hexa-atomic aromatic heterocycle that the haloalkyl substituting group replaces;
L is halogen or methyl;
X is a fluorine;
Y is chlorine or fluorine;
Z is a hydrogen, fluorine or methyl;
M is a numerical value 0,1,2,3,4 or 5;
N is numerical value 0,1 or 2 Hes
R 1Be hydrogen, C 1-C 4Alkyl, thiophenyl or toluene sulfenyl.
2. according to the compound of claim 1, the A in its Chinese style is an oxygen.
3. according to the compound of claim 1 or 2, the B in its Chinese style is an ethylene bridge.
4. according to the compound of claim 1, the A in its Chinese style is-the NH-bridge.
5. according to any one compound in claim 1 and 4, the n in its Chinese style is 0.
6. according to the compound of claim 1, the D in its Chinese style is-O-.
7. according to any one compound in the claim 1,2,4 and 6, the E in its Chinese style is a phenyl, pyridyl, and thiadiazolyl group is selected from cyano group, nitro, halogen, C by 1 or 2 1-C 4Alkyl and C 1-C 4The phenyl that the haloalkyl substituting group replaces is selected from halogen, C by 1 or 2 1-C 4Alkyl and halo C 1-C 4The pyridyl that alkyl substituent replaces, or C 1-C 4-alkyl thiazolyl.
8. according to any one compound in the claim 1,2,4 and 6, the m in its Chinese style is a numeral 0,1 or 4.
9. according to the compound of claim 1 or 2, the Y in its Chinese style is that fluorine and Z are hydrogen.
10. according to the compound of claim 1, D is-O-CH in formula 2-.
11. according to the compound of claim 1, the D in its Chinese style is-O-CO-or-O-CO-O-.
12. according to the compound of claim 2, the n in its Chinese style is 0.
13. according to the compound of claim 12, the D in its Chinese style is oxygen or sulphur.
14. according to the compound of claim 2, the D in its Chinese style is-O-CH 2
15. according to the compound of claim 6, the E in its Chinese style is phenyl, thiadiazoles or a pyridyl replacement or unsubstituted.
16. according to the compound of claim 3, the A in its Chinese style is an oxygen, n be the numeral 0, D is an oxygen, sulphur or-O-CH 2-, E is a phenyl, pyridyl, and thiadiazolyl group is selected from cyano group, nitro, halogen, C by 1 or 2 1-C 4Alkyl and C 1-C 4The phenyl that the haloalkyl substituting group replaces is selected from halogen, C by 1 or 2 1-C 4Alkyl and halo-C 1-C 4The pyridyl that alkyl substituent replaces; Or C 1-C 4Alkyl thiazolyl, m are numerals 0,1 or 4, and Y is that fluorine and Z are hydrogen.
17. according to the compound of claim 16, the X in its Chinese style is a fluorine, Y is a fluorine, and Z is a hydrogen, and m is 1, and A is an oxygen, and B is-CH 2CH 2-, n is 0, D-E is-O-CH 2-E and E are the 4-trifluoromethyls.
18. according to the compound of claim 1, wherein this compound is selected from following material:
4,4-two fluoro-3-butenoic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
4,4-two fluoro-3-butenoic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
4,4-two fluoro-3-butenoic acid 2-(4-(4-methyl benzyloxy) phenoxy group) ethyl ester,
6,6-two fluoro-5-hexenoic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
6,6-two fluoro-5-hexenoic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
8,8-two fluoro-7-octylenic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
8,8-two fluoro-7-octylenic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
10,10-two fluoro-9-decylenic acid 2-(4-phenoxy group phenoxy group) ethyl esters,
10,10-two fluoro-9-decylenic acid 2-(4-benzyloxy phenoxy group) ethyl esters,
12,12-two fluoro-11-dodecylene 2-(4-phenoxy group phenoxy group) acetic ester and
12,12-two fluoro-11-dodecenoic acid 2-(4-benzyloxy phenoxy group) ethyl esters.
19. the preparation method of the compound of claim 1, it comprises
A) compound shown in compound shown in the formula (II) and the formula (III) or
Its salt is using or is not using inert solvent, reacts in the presence of acid binding agent
Figure C9310784700051
X in formula (II), Y, Z and m determine that suc as formula I Hal is a chlorine or bromine,
Figure C9310784700052
A in formula (III), B, L, D, E and n determine suc as formula I, or b) compound or its salt shown in compound shown in the formula V and the formula (III) reacts under the condition of using or do not use inert solvent, catalyzer or dewatering agent
Figure C9310784700053
X in formula V, Y, Z and m determine suc as formula I,
Under each situation, the free cpds shown in the formula I that will obtain by the preparation method transforms salify if desired, maybe the salt shown in the formula I that obtains by the preparation method can be transformed free cpds shown in the accepted way of doing sth I or different salt.
20. pesticide composition wherein contains and is the compound and at least a auxiliary agent of available salt form on free form or the agrochemistry as effective constituent shown in the formula I of at least a claim 1.
21. a control harmful organism method, it comprises and is applied to harmful organism or their environment as the compound shown in the formula I of effective constituent with available salt form on free form or the agrochemistry with claim 1 is described.
22. according to the method for claim 21, wherein this method is used to pest control and/or arachnoide pest.
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